Process for dyeing or printing hydroxyl group containing fiber materials

ABSTRACT

The invention relates to a process for dyeing or printing hydroxyl group containing fiber materials, which comprises using at least one yellow or orange dyeing dye of formula ##STR1## wherein the substituents are as defined in claim 1, together with at least one blue dyeing dye and/or at least one red dyeing dye. Level dyeings and prints with good allround fastness properties are obtained by the process of the invention.

This application is a continuation of application Ser. No. 08/231,966, filed Apr. 22, 1994, now abandoned, which is a continuation of Ser. No. 07/991,671 filed Dec. 16, 1992, now abandoned.

The present invention relates to a process for dyeing or printing hydroxyl group containing fibre materials with dye mixtures by the dichromatic or trichromatic dyeing technique.

Dyeing or printing textile materials by the dichromatic or trichromatic technique requires, inter alia, the use of dyes that have as level a build-up as possible while at the same time having consistency of shade in different concentrations and good compatibility in order to obtain dyed or printed textile materials which substantially meet the demands made of them.

This object was not always achieved with the dyes and dye mixtures used heretofore, especially with respect to compatibility, uptake, fibre levelness and surface levelness, as well as allround fastness properties such as wetfastness. Hence it is the object of this invention to provide improved processes for dyeing and printing hydroxyl group containing fibre materials by the dichromatic or trichromatic dyeing technique.

It has now been found that the inventive process meets the aforementioned requirements.

Accordingly, the invention relates to a process for dyeing or printing hydroxyl group containing fibre materials, which comprises using at least one yellow or orange dyeing dye of formula ##STR2## wherein X₁ and X₂ are each a radical of the naphthalene series and R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, together with at least one blue dyeing dye and/or at least one red dyeing dye.

Halogen substituents R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ in formula (1) are each independently of one another fluoro, bromo or, preferably, chloro.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ in formula (1) deemed as C₁ -C₈ alkyl are typically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl and octyl. Preferably R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are C₁ -C₄ alkyl.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ deemed in formula (1) as C₁ -C₄ alkoxy are preferably C₁ -C₄ alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ deemed as C₂ -C₆ alkanoylamino in formula (1) are preferably C₂ -C₄ alkanoylamino, typically acetylamino or propionylamino. C₂ -C₆ Alkanoylamino as C₂ -C₆ alkanoylamino which is substituted in the alkyl moiety is typically carboxy- or, preferably, hydroxy-substituted.

X₁ and X₂ as radicals of the naphthalene series are unsubstituted naphthalene radicals or naphthalene radicals which are substituted typically by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₄ alkanoylamino, preferably by sulfo.

It is preferred to use dyes of formula (1), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo, preferably hydrogen or sulfo.

It is especially preferred to use dyes of formula (1), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen or sulfo and X₁ and X₂ are unsubstituted naphthalene radicals or naphthalene radicals which are substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₄ alkanoylamino, preferably by sulfo.

It is most especially preferred to use as dyes of formula (1) dyes of formula ##STR3## wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ have the meanings and preferred meanings given above and R₉ and R₁₀ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo, preferably hydrogen or sulfo,

Particularly interesting dyes of formula (1) for the process of this invention are the dyes of formula ##STR4## wherein R₉ and R₁₀ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo, preferably hydrogen or sulfo.

The most preferred dye of formula (1) for the process of the invention is the dye of formula ##STR5##

As blue dyeing dyes it is preferred to use in the inventive process at least one dye of formulae (5), (6) and (7) ##STR6## wherein D₁ is unsubstituted or substituted phenyl or naphthyl, R₁₁, R₁₂, R₁₃ and R₁₄ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety and R₁₅ is hydrogen, unsubstituted or substituted C₁ -C₈ alkyl, C₂ -C₆ alkanoyl which is unsubstituted or substituted in the alkyl moiety, or phenyl or benzoyl which are unsubstituted or substituted in the phenyl ring ##STR7## wherein D₂ and D₃ are unsubstituted or substituted naphthyl, and R₁₆ and R₁₇ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, ##STR8## wherein R₁₈, R₁₉ and R₂₀ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, and R₂₁ is unsubstituted or substituted C₁ -C₈ alkyl or phenyl.

Halogen substituents R₁₁, R₁₂, R₁₃ and R₁₄ in formula (5), R₁₆ and R₁₇ in formula (6) and R₁₈, R₁₉ and R₂₀ in formula (7) are each independently of one another typically fluoro, bromo or, preferably, chloro.

R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ in formula (5), R₁₆ and R₁₇ in formula (6) and R₁₈, R₁₉, R₂₀ and R₂₁ in formula (7) defined as unsubstituted or substituted C₁ -C₈ alkyl are preferably C₁ -C₄ alkyl, typically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, as well as the radicals substituted by e.g. C₁ -C₄ alkoxy, C₁ -C₄ alkoxycarbonyl, hydroxy, halogen such as chloro or fluoro, carboxy, cyano, sulfo or sulfato.

R₁₁, R₁₂, R₁₃ and R₁₄ in formula (5), R₁₆ and R₁₇ in formula (6) and R₁₈, R₁₉ and R₂₀ in formula (7) defined as unsubstituted or substituted C₁ -C₈ alkoxy are preferably C₁ -C₄ alkoxy, typically methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, as well as the hydroxy- or carboxy-substituted radicals.

R₁₁, R₁₂, R₁₃ and R₁₄ in formula (5), R₁₆ and R₁₇ in formula (6) and R₁₈, R₁₉ and R₂₀ in formula (7) defined as C₂ -C₆ alkanoylamino are preferably C₂ -C₄ alkanoylamino, typically acetylamino or propionylamino. C₂ -C₆ Alkanoylamino which is substituted in the alkyl moiety may suitably be hydroxy-substituted.

R₁₅ as C₂ -C₆ alkanoyl in formula (5) is preferably C₂ -C₄ alkanoyl, typically acetyl or propionyl. C₂ -C₆ Alkanoyl which is substituted in the alkyl moiety may suitably be hydroxy-substituted.

The substituents D₁ defined as phenyl or naphthyl, D₂ and D₃ as naphthyl, R₁₅ as phenyl or benzoyl as well as R₂₁, as phenyl may be unsubstituted or substituted. Typical examples of substituents are halogen, amino, sulfo, carboxy, ureido, C₂ -C₄ alkanoylamino which may be further substituted in the alkyl moiety by hydroxy, C₁ -C₄ alkyl, C₁ -C₄ alkoxy which may be further substituted by hydroxy or carboxy, as well as benzoylamino or phenylamino which may be further substituted in the phenyl ring by carboxy, halogen, sulfo, C₁ -C₄ alkyl or C₁ -C₄ alkoxy.

As blue dyeing dyes it is preferred to use for the inventive process at least one dye of formulae ##STR9## especially the dye of formula (8).

As red dyeing dyes it is preferred to use for the inventive process at least one dye of formulae (12), (13), (14), (15) and (16) ##STR10## wherein R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ and R₂₇ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, and A₃ is a radical of formula ##STR11## wherein R and R' are hydrogen or unsubstituted or substituted C₁ -C₈ alkyl, and Y₃ is hydroxy, C₁ -C₄ alkoxy, chloro, bromo, C₁ -C₄ alkylthio, amino, N-mono- or N,N-di-C₁ -C₄ alkylamino which is unsubstituted or substituted in the alkyl moiety or moieties by hydroxy, sulfo, carboxy or C₁ -C₄ alkoxy, cyclohexylamino, phenylamino or N-C₁ -C₄ alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl nucleus by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, carboxy, sulfo and/or halogen, or are morpholino or 3-carboxy- or 3-carbamoylpyridin-1-yl, ##STR12## wherein R₂₈, R₂₉, R₃₀ and R₃₁ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido, sulfamoyl or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, and A₄ is as defined for A₃ under formula (12), ##STR13## wherein R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ ale hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, and R₃₉ is benzoylamino or benzoylamino which is substituted in the phenyl ring, or a radical of formula ##STR14## which may be further substituted in the phenyl ring, wherein R and R' are hydrogen or unsubstituted or substituted C₁ -C₈ alkyl and Y₄ is as defined for Y₃ under formula (12), ##STR15## wherein R₄₀, R₄₁, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆ and R₄₇ are hydrogen, unsubstituted or substituted C₁ -C₄ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, and R₄₀ and R₄₆ may additionally be phenylazo or phenylazo which is substituted in the phenyl ring, and A₅ is as defined for A₃ under formula (12), or is a radical of formula ##STR16## wherein R and R' are hydrogen or unsubstituted or substituted C₁ -C₈ alkyl and Y₅ is as defined for Y₃ under formula (12), ##STR17## wherein R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ and R₅₄ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted in the alkyl moiety, and A₆ is as defined for A₃ under formula (12).

Halogen substituents R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ and R₂₇ in formula (12), R₂₈, R₂₉, R₃₀ and R₃₁ in formula (13), R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ in formula (14), R₄₀, R₄₁, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆ and R₄₇ in formula (15), and R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ and R₅₄ in formula (16) are each independently of one another typically fluoro, bromo or, preferably, chloro.

Unsubstituted or substituted C₁ -C₈ alkyl cited above as substituent of the dyes of formulae (12) to (16) as well as suitable value for R and R' is preferably C₁ -C₄ alkyl, typically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, as well as the radicals substituted by e.g. C₁ -C₄ alkoxy, C₁ -C₄ alkoxycarbonyl, hydroxy, halogen, typically chloro or fluoro, carboxy, cyano, sulfo or sulfato.

Preferably R and R' have the same meanings. R and R' are preferably hydrogen or C₁ -C₄ alkyl, most preferably hydrogen.

Unsubstituted or substituted C₁ -C₈ alkoxy cited above as substituents of the dyes of formulae (12) to (16) is preferably C₁ -C₄ alkoxy, typically methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, as well as the hydroxy- or carboxy-substituted radicals.

C₂ -C₆ Alkanoylamino cited above as substituent of the dyes of formulae (12) to (16) is preferably C₂ -C₄ alkanoylamino, typically acetylamino or propionylamino. C₂ -C₆ alkanoylamino which is substituted in the alkyl moiety may suitably be hydroxy-substituted.

R₃₉ as benzoylamino or as radical of formula ##STR18## as well as R₄₀ and R₄₆ as phenylazo may be unsubstituted or substituted in the phenyl ring. Typical examples of substituents are halogen, amino, sulfo, carboxy, ureido, C₂ -C₄ alkanoylamino which may be further substituted in the alkyl moiety by hydroxy, C₁ -C₄ alkyl, C₁ -C₄ alkoxy which may be further substituted by hydroxy, as well as benzoylamino or phenylamino which may be further substituted in the phenyl ring by carboxy, halogen, sulfo, C₁ -C₄ alkyl or C₁ -C₄ alkoxy. Preferred substituents are halogen, sulfo or C₁ -C₄ alkyl.

Typical examples of substituents Y₃, Y₄ and Y₅ are hydroxy, methoxy, ethoxy, n- or isopropoxy, chloro, methylthio, ethylthio, amino, methylamino, ethylamino, carboxymethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, phenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-sulfophenylamino, 2,4- or 2,5-disulfophenylamino, o-carboxyphenylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino and morpholino.

Preferably Y₃, Y₄ and Y₅ are each independently of one another chloro, amino, N-mono- or N,N-di-C₁ -C₄ alkylamino which are unsubstituted or hydroxy-substituted in the alkyl moiety or moieties, or are phenylamino or morpholino, preferably morpholino or chloro.

As red dyeing dyes it is preferred to use for the inventive process at least one dye of formula ##STR19## especially a dye of formula (17).

It is particularly preferred to use at least one yellow or orange dyeing dye of formula (1) together with at least one blue dyeing dye of formulae (5) to (7) and/or at least one red dyeing dye of formulae (12) to (16). As blue dyeing dyes those of formulae (5) and (7), and as red dyeing dyes those of formulae (13), (15) and (16), merit particular interest.

In the process of this invention it is especially preferred to use at least one yellow or orange dyeing dye of formula (1), preferably a yellow or orange dyeing dye of formulae (4), together with at least one blue dyeing dye of formulae (8), (9), (10), (11) and (11a) and/or at least one red dyeing dye of formulae (17) to (21), the blue dyeing dye being preferably the dye of formula (8) and the red dyeing dye preferably being the dye of formula (17).

A particularly important embodiment of the process of this invention comprises using a yellow or orange dyeing dye of formula (4) together with a blue dyeing dye of formula (8) and/or a red dyeing dye of formula (17).

The process of this invention is particularly suitable for trichromatic or dyeing or printing using at least one yellow or orange dyeing dye of formula (1) together with at least one blue dyeing dye and at least one red dyeing dye. With respect to the dyes used for trichromatic dyeing or printing, the meanings and preferred meanings previously given above apply.

By trichromatic dyeing is meant the additive blending of suitably chosen yellow or orange, red and blue dyeing dyes in the concentrations necessary for obtaining the desired shade.

The yellow or orange dyeing dyes of formula (1), the blue dyeing dyes of formulae (5) to (7) and the red dyeing dyes of formulae (12) to (16) are known or they can be prepared by methods analogous to those for obtaining known dyes.

With respect to their tinctorial properties, the yellow or orange dyeing dyes of formula (1), the blue dyeing dyes of formulae (5) to (7) and the red dyeing dyes of formulae (12) to (16) used in the process of this invention may be termed direct dyes (C.I. direct dyes).

The yellow or orange dyeing dyes of formula (1), the blue dyeing dyes and the red dyeing dyes used in the inventive process are either in the form of their free sulfonic acid or, preferably, as salts thereof, typically as alkali metal salts, alkaline earth metal salts or ammonium salts or as salts of an organic amine. Typical examples are the sodium, potassium, lithium or ammonium salts or the salt of triethanolamine.

For the inventive process, the concentrations in which the yellow or orange dyeing dyes of formula (1), the blue dyeing dyes and the red dyeing dyes are used in the dyebaths or printing pastes vary, depending on the desired depth of shade. In general, concentrations of 0.01 to 10 percent by weight, preferably of 0.1 to 6 percent by weight, based on the material to be dyed, have been found useful.

Suitable hydroxyl group containing fibre materials, especially textile materials, which can be dyed or printed by the process of the invention are typically those made from cellulosic fibres such as cotton, linen or hemp, preferably cotton, as well as regenerated cellulose fibres such as viscose rayon, rayon or viscose staple fibres.

Hydroxyl group containing fibre materials will also be understood as meaning blends containing such fibre materials. Suitable blends are typically those containing, in addition to cellulosic fibre materials, natural or synthetic polyamide fibre materials or acrylic or polyester fibre materials. Exemplary of such blends are wool/cotton, polyamide/cotton, acrylic/cotton or, preferably, polyester/cotton blends.

The textile materials can be in any form of presentation, typically as fibres, yarn, woven or knitted goods.

The process of the invention is suitable for dyeing by the exhaust or the pad method as well as for printing by the standard methods employed.

Dyeing by the exhaust method is preferred. Exhaust dyeing is normally carded out in the temperature range from 60° to 110° C., preferably from 90° to 105° C., in the pH range from 6 to 10, preferably from 7 to 9, preferably from an aqueous liquor at a liquor to goods ratio of 1:5 to 1:80, most preferably of 1:10 to 1:20.

A particularly preferred embodiment of the inventive process comprises dyeing in the presence of a salt, conveniently in the presence of an alkali metal halide, preferably an alkali metal chloride, or of an alkali metal sulfate. A portion of the salt is preferably added at the start of the dyeing process and then a further portion is added, altogether or in increments, shortly before or after the dyeing temperature has been reached. The amount of salt added at the start of the dyeing process is normally from 5 to 40% of the total amount of salt added in the course of the dyeing process. The mount of salt added shortly before or after the dyeing temperature has been reached is thus 60 to 95% of the total amount of salt added in the course of the dyeing process. The temperature range shortly before dyeing temperature is reached will be understood as meaning the heating up range for attaining the dyeing temperature, typically the temperature range from 80° to 98° C. It is preferred to add the salt direct when the dyeing temperature is reached. In this embodiment of the inventive process it has been found useful to add a total amount of salt depending on the total amount of the dyes used. Normally the total amount of salt added will increase with the total amount of the dyes. The amount of salt added is typically 6 to 12 g/l up to a total amount of 1% of dye, typically 12 to 20 g/l up to a total amount of 2% of dye, and typically 20 to 40 g/l above a total amount of 2% of dye. The dye concentrations are here expressed in percentages by weight, based on the fibre material, and normally correspond to the dyes obtained after their synthesis, conveniently by salting out.

Dyeing by the exhaust method is preferred for this embodiment of the inventive process.

It is also possible to dye textile fibre materials made from blends, typically from wool/cotton, polyamide/cotton, acrylic/cotton or, preferably polyester/cotton blends by one bath processes and in the presence of dyes for the other different type of fibre component.

It is thus possible to dye blends of synthetic fibres and cellulosic fibre materials, preferably polyester/cotton blends, in the presence of a disperse dye for the synthetic fibre component under the dyeing conditions for synthetic fibres. Suitable synthetic fibres are preferably polyester fibres. If dyeing is carried out in this embodiment of the process in the presence of a salt such as an alkali metal halide or an alkali metal sulfate, then it is preferred to add the total amount of salt at the start of the dyeing process.

The dyes used for the inventive process have good compatibility with other dyes, especially disperse dyes. They have a sufficient high-temperature stability and can hence be used for dyeing under the dyeing conditions for polyester fibres, i.e. in the temperature range from about 100° to 150° C., preferably from 120° to 130° C., from an aqueous liquor and in the pH range from about 4 to 7.5, preferably from 5 to 7.

It is thus possible to use conventional disperse dyes together with the dyes eligible for the process of this invention in a single step, one bath process for dyeing polyester/cotton blends, in which process level and fast dyeings are obtained with the respective dye on both fibre components. By using a disperse dye of the same shade as the dye mixture used for the inventive process, it is also possible to obtain solid shade dyeings.

The dyeing of textile blends, typically blends of polyester and cellulosic fibres, can be greatly simplified in this embodiment of the inventive process. The conventional practice of dyeing each component of a fibre blend in a separate procedure under different dyeing conditions is therefore no longer necessary.

The dyes used for the process of this invention are distinguished by level colour build-up while having consistency of shade at different concentrations and good compatibility with other dyes. The dyeings and prints obtained have good fibre levelness and surface levelness and good allround fastness properties, especially good fastness to rubbing, wet treatments, wet rubbing, perspiration and light. Where necessary, the wetfastness properties, especially the washfastness, can be further substantially enhanced by an aftertreatment with fixing alkalies. Examples of suitable fixing alkalies are those described in EP-A-250 265 and EP-A-438 380.

The invention is illustrated by the following Examples in which parts and percentages are by weight, unless otherwise indicated. The relationship between parts by weight and parts by volume is the same as that between the kilogram and the liter.

EXAMPLE 1

12.5 parts of non-mercerised cotton fabric are wetted with one part of a non-ionic wetting agent at 80° C. The pretreated cotton fabric is pinched off and put into a warm dye solution of 40° C. which contains, in deionised water, 0.1% of the yellow dyeing dye of formula ##STR20## 0.17% of the red dyeing dye of formula ##STR21## and 0.13% of the blue dyeing dye of formula ##STR22## based on the weight of the cotton fabric, at a liquor ratio of 1:10. The dyebath is kept for 5 minutes at a temperature of 40° C., then 1.2 g/l of sodium sulfate are added and, after a further 5 minutes, the temperature of the dyebath is raised to boiling temperature at a heating-up rate of 1.5° C./minute. When boiling temperature is reached, 4.8 g/l of sodium sulfate are added and the dyebath is kept for 45 minutes at c. 98° C. Then the dyebath is cooled to c. 80°-85° C. at a cooling rate of 1° C./minute and kept for 15 minutes at this temperature. The dyed fabric is then removed from the bath, washed twice for 5 minutes with water, pinched off and dried in a drying oven at c. 80°-90° C. The cotton is dyed in a level grey-brown shade of good allround fastness properties. The fastness properties, especially the washfastness, are enhanced by subjecting the dyed cotton fabric to an aftertreatment with a cationic fixing agent.

EXAMPLES 2 to 20

The procedure of Example 1 is repeated, but replacing 0.1% of the yellow dyeing dye of formula (101), 0.17% of the red dyeing dye of formula (102) and 0.13% of the blue dyeing dye of formula (103) with the dyes listed in column 2 of the following Table in the given concentrations, and using instead of 1.2 g/l of sodium sulfate the amount of sodium sulfate A indicated in column 3, and instead of 4.8 g/l of sodium sulfate the amount of sodium sulfate B indicated in column 4, to give a cotton fabric dyed in the shade indicated in column 5. The dyes of formulae (104) to (110) specified in column 2 are listed after the Table.

    ______________________________________                                                            Sodium   Sodium                                                                sulfate  sulfate                                            Ex.  Dyes          A        B       Shade                                      ______________________________________                                          2   0.6% of the dye of                                                                           3.0 g/l  19.0 g/l                                                                               grey-brown                                      formula 101)                                                                   0.42% of the dye                                                               formula (103)                                                                  0.74% of the dye of                                                            formula (104)                                                              3   0.54% of the dye of                                                                          1.7 g/l  15.3 g/l                                                                               brown-orange                                    formula (101)                                                                  0.78% of the dye of                                                            formula (102)                                                                  0.028% of the dye of                                                           formula (103)                                                              4   0.12% of the dye of                                                                          7.5 g/l  17.5 g/l                                                                               red violet                                      formula (101)                                                                  1.14% of the dye of                                                            formula (104)                                                                  1.51% of the dye of                                                            formula (105)                                                              5   0.258% of the dye of                                                                         1.5 g/l   4.5 g/l                                                                               olive green                                     formula (101)                                                                  0.16% of the dye of                                                            formula (103)                                                              6   0.258% of the dye of                                                                         1.0 g/l   7.0 g/l                                                                               orange                                          formula (101)                                                                  0.24% of the dye of                                                            formula (102)                                                              7   0.086% of the dye of                                                                         1.0 g/l   6.0 g/l                                                                               grey                                            formula (101)                                                                  0.12% of the dye of                                                            formula (102)                                                                  0.24% of the dye of                                                            formula (103)                                                              8   0.5% of die dye of                                                                           4.0 g/l  15.0 g/l                                                                               brown-                                          formula (101)                  orange                                          0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             formula (105)                                                              9   0.5% of the dye of                                                                           5.0 g/l  15.0 g/l                                                                               greenish-                                       of formula(101)                grey olive                                      0.5% of the dye of                                                             formula (103)                                                                  0.5% of the dye of                                                             formula (105)                                                             10   0.5% of the   6.0 g/l  13.0 g/l                                                                               brown-                                          formula (101)                  violet                                          0.5% of the dye of                                                             formula (106)                                                                  0.5% of the dye of                                                             formula (105)                                                             11   0.5% of the dye of                                                                           7.0 g/l  11.0 g/l                                                                               orange                                          formula (101)                                                                  0.5% of the dye of                                                             formula (107)                                                                  0.5% of the dye of                                                             formula (105)                                                             12   0.5% of the dye of                                                                           3.5 g/l  14.5 g/l                                                                               grey-olive                                      formula (101)                                                                  0.5% of the dye of                                                             formula (108)                                                                  0.5% of the dye of                                                             formula (105)                                                             13   0.5% of the dye of                                                                           3.0 g/l  16.0 g/l                                                                               greenish-                                       formula(101)                   grey olive                                      0.5% of the dye of                                                             formula (109)                                                                  0.5% of the dye of                                                             formula (105)                                                             14   0.5% of the dye of                                                                           3.5 g/l  15 g/l  anthracite                                      formula (101)                                                                  0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             formula (109)                                                             15   0.5% of the dye of                                                                           4.0 g/l  14.0 g/l                                                                               brown-                                          formula (101)                  orange                                          0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             of formula (107)                                                          16   0.5% of the dye of                                                                           4.0 g/l  15.0 g/l                                                                               brown-                                          formula (101)                  violet                                          0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             formula (106)                                                             17   0.5% of the dye of                                                                           5.0 g/l  13.5 g/l                                                                               brown                                           formula (101)                                                                  0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             formula (103)                                                             18   0.5% of the dye of                                                                           6.0 g/l  12.0 g/l                                                                               brown                                           der Formel (101)                                                               0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             formula (108)                                                             19   0.5% of the dye of                                                                           3.5 g/l  15.5 g/l                                                                               brown                                           formula (101)                                                                  0.5% of the dye of                                                             formula (104)                                                                  0.5% of the dye of                                                             formula (110)                                                             20   0.5% of the dye of                                                                           4 g/l    15.5 g/l                                                                               reddish                                         formula (101)                  brown                                           0.5% of the dye of                                                             formula (102)                                                                  0.5% of the dye of                                                             formula (110)                                                             ______________________________________                                    

List of dyes of formulae (104) to (110) indicated in the above Table: ##STR23##

EXAMPLE 21

250.8 parts of thoroughly wetted polyester/cotton knit goods comprising 30 parts of polyester and 70 parts of cotton per 100 parts are put at 60° C. into a high-temperature jet dyeing machine. The liquor ratio is 1:7. The following auxiliaries are then added to the dyebath:

0.75 g/l of a commercially available lubricant (oxyalkylene-polyester condensate type),

0.3 g/l of a maleate-based silicone-free penetration accelerator,

1 g/l of a levelling assistant (ammonium salt of an acid-modified polyhydroxy alkylene glycol ether),

2 g/l of monosodium dihydrogen phosphate buffer,

2 g/l of sodium-m-nitrobenzenesulfonate and

10 g/l of sodium sulfate.

The pH is adjusted to 5 with acetic acid. The dye liquor is kept for 5 minutes at 60° C. and then a mixture of 0.74 part of the dye of formula (101), 0.45 part of the dye of formula (102), 0.48 part of the dye of formula (103), 0.21 part of a yellow dyeing disperse dye of formula ##STR24## 0.19 part of a red dyeing disperse dye of formula ##STR25## and 0.17 part of a blue dyeing disperse dye of formula ##STR26## are added to the dyebath. The dyebath is then heated to 130° C. at a heating-up rate of 2° C./minute, kept at this temperature for 30 minutes and thereafter cooled to 80° C. at a cooling rate of 1.5° C./minute. The dyebath is kept for 15 minutes at 80° C., then drained off and the dyed material is washed twice for 5 minutes with warm water of 30° C. The dyeing is finished by drying in conventional manner or treated with a cationic aftertreating agent. Suitable aftertreating agents include those based on polymerised quaternary diallylammonium compounds, typically the compounds described in EP-A-438 380. The material is dyed in a light olive brown shade of excellent levelness. 

What is claimed is:
 1. A process for dyeing or printing a cellulosic fibre material, which comprises applying to said fibre material at least one yellow or orange dyeing dye of formula ##STR27## wherein R₉ and R₁₀ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo;together with at least one of the blue dyeing dyes of formulae ##STR28## and together with at least one of the red dyeing dyes of formulae ##STR29##
 2. A process according to claim 1, wherein the dye of formula (3) is a dye of formula ##STR30##
 3. A process according to claim 1, which comprises using one yellow dyeing dye of formula ##STR31## together with at least one of the blue dyeing dyes of formulae ##STR32## and at least one of the red dyeing dyes of formulae ##STR33##
 4. A process according to claim 1, wherein dyeing is carried out in the presence of a salt, a portion of said salt being added at the start of the dyeing process and a further portion being added all at once or in increments shortly before or after the dyeing temperature has been reached.
 5. A process according to claim 4, wherein the total amount of salt added depends on the total amount of dye used.
 6. A process according to claim 1, which comprises dyeing blends of synthetic fibres and cellulosic fibre materials, in the presence of a disperse dye for the synthetic fibre component under the dyeing conditions for synthetic fibres.
 7. A process according to claim 6, which comprises dyeing polyester/cotton blends in a one-step, single bath process, using a disperse dye in addition to the trichromatic dye mixture and dyeing from an aqueous liquor in the temperature range from 100° to 150° C., and in the pH range from 4 to 7.5.
 8. A process of claim 3 wherein the yellowing dyeing dye is of formula (4), the blue dyeing dye is of formula (8) and the red dyeing dye is of formula (17).
 9. A process of claim 4 wherein the salt is an alkali metal halide or an alkali metal sulfate.
 10. A process of claim 5 wherein the fiber material is a polyester/cotton blend.
 11. A process of claim 6 wherein the temperature is from 120° to 130° C. 